CN108129651A - A kind of method for preparing cardanol polyoxyethylene ether - Google Patents
A kind of method for preparing cardanol polyoxyethylene ether Download PDFInfo
- Publication number
- CN108129651A CN108129651A CN201710997443.6A CN201710997443A CN108129651A CN 108129651 A CN108129651 A CN 108129651A CN 201710997443 A CN201710997443 A CN 201710997443A CN 108129651 A CN108129651 A CN 108129651A
- Authority
- CN
- China
- Prior art keywords
- polyoxyethylene ether
- anacardol
- cardanol polyoxyethylene
- raw material
- ethylene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyethers (AREA)
Abstract
The present invention provides a kind of methods for preparing cardanol polyoxyethylene ether.In voltage-resistant reactor, raw material anacardol and ethylene oxide under alkoxide catalysis effect, in the case where heating pressurized conditions, complete polymerisation in 2~4h.Then reaction mass is cooled down, is neutralized with lactic acid, obtain cardanol polyoxyethylene ether.Traditional inorganic strong alkali is replaced due to the use of alkoxide（Such as NaOH, KOH）To make catalyst and usually used acetic acid is replaced to make neutralizer with lactic acid, make the stable polymerization reaction controllable, products obtained therefrom lighter color, molecular weight distribution is relatively narrow, and rheological characteristic is good, thus with good application performance.The method of the present invention is strong to adaptability to raw material.Commercially available unsaturation anacardol raw material, can give direct use.According to using needs, the adjustable ethylene oxide molecule number for needing addition, so as to adjust product Pro You Pro water balances（HLB value）, to produce the functional products such as the emulsifier, wetting dispersing agent, detergent, the levelling agent that are suitable for corresponding field.
Description
Technical field
Biomass material anacardol is the present invention relates to the use of, carries out ethoxylation polyaddition reaction, it is a kind of non-to produce
Ionic surface active agent.Present invention ownership polymer synthetic chemistry and fine chemical technology scope.
Background technology
Anacardol (cardanol) is produced by cashew nut shell liquid processing.It is a kind of very rare natural biomass
Phenol, it in chemical synthesis may be substituted petroleum base phenols raw material, produced applied to chemistry with its unique structural behaviour
The macromolecule new material in the fields such as building materials, car and boat construction, aerospace, telecommunications.Anacardol is in thermoset epoxy at present
It is preferably applied in the synthesis of polymer materials such as resin, phenolic resin.
With scientific and technological progress and industrial development, the production of surfactant has obtained corresponding development to application.Especially
It is nonionic surfactant, and the development by petrochemical industry, Ethylene Industry is even more to advance by leaps and bounds.Although non-ionic surface
Activating agent has it because its structure feature (containing hydroxyl and ehter bond Liang Zhong Pro hydratase genes in molecule) is compared with ionic surfactant
More good characteristic such as has preferable dissolubility and low bubble in water, relatively stablizes in the solution, there is preferable electrolyte-resistant,
Acid-fast alkali-proof.Also, it is good with other types of surfactant compatibility, matched can use.Therefore, it is each
Kind industry and civil field are widely applied.However, with petroleum base alkyl phenol (such as octyl phenol, nonyl phenol) for initiator
Alkyl phenol polyoxyethylene ether (such as OP, NP) obtained, in the industrial wastewater generated after use, under natural environmental condition
Biodegradation is difficult to, causes environmental pollution.In some developed countries, these alkyl phenol polyether products are disabled now.Therefore
Research and development are just being happened at that time using natural biological base alkyl phenol-anacardol as the polyoxyethylene ether product of initiator, of far-reaching significance.
Because it is originated from the Nature life and growth in nature, and biodegradable, human ecological environment is takeed good care of, is green chemical products.
Domestic and international expert has made compared with in-depth study the synthetic technology of cardanol polyoxyethylene ether.Chinese patent
CNI01941894A (its denomination of invention：A kind of cardanol polyoxyethylene ether and preparation method thereof) it introduces, with anacardol and epoxy
Ethane is raw material, and potassium hydroxide is catalyst, is neutralized after reaction with acetic acid.This method reaction condition is mild, by-product in products obtained therefrom
Object is few, and product color is good.But the inherent qualities factor such as product molecular weight distribution is not referred to.Chinese patent CN102351664A (its
Denomination of invention：The preparation method of pentadecyl phenol polyethenoxy ether strong biodegradable surfactant) it introduces, depickling is used respectively
The isolated single phenol of cashew nut shell stoste (containing single phenol and bis-phenol), rectifying and bis-phenol and its hydrogenation saturated products, in base catalysis
Agent (NaOH, KOH) effect is lower to be made corresponding cardanol polyoxyethylene ether product with reacting ethylene oxide, the 7th day
Biological degradability is 100%.Chinese patent 103449984A (its denomination of invention：A kind of cardanol polyoxyethylene ether and its preparation
Method) it reveals, the double bond retention rate that product is made for catalyst using metallic sodium, potassium is high (＞ 95%), good product quality, property
It can stablize.
Invention content
The purpose of the present invention is intended to provide a kind of more practical method for preparing cardanol polyoxyethylene ether, to avoid oil
Pollution of the base alkyl phenol polyoxyethylene ether to environment promotes the formation of anacardol industrial chain.
A kind of cardanol polyoxyethylene ether prepared by the present invention has following molecular structure (formula 1)：
Wherein, n=2~30
R is the hydrocarbon chain containing 15 carbon atoms, can be the saturated hydrocarbon chain that is expressed as below or containing monoene, diene, triolefin respectively
Aliphatic unsaturated hydrocarbon：C15H31, C15H29, C15H27, C15H25.
Preparation method now with such as a kind of cardanol polyoxyethylene ether of 1 molecular structure of formula is described as follows：It is resistance to one
It presses in reactor, puts into marketable material anacardol and alkoxide catalysis, with inflated with nitrogen and vacuumize air in metathesis reactor
3~4 times, then agitating and heating is in 90~120 DEG C of vacuum dehydrations.Start to be gradually added ethylene oxide under certain negative pressure.Control
For reaction temperature in 130~165 DEG C, pressure is 0.1~0.3MPa.After ethylene oxide adds, maintain to occur in reaction to reactor
Negative pressure (about 1h).Then material is cooled down, is discharged after being neutralized to subacidity with lactic acid, cardanol polyoxyethylene ether is made.
With it is existing prepare the technology of cardanol polyoxyethylene ether compared with, the method for the present invention uses commercially available unsaturated anacardol
Raw material (sees attached list 3, anacardol quality analysis list).Any refinement treatment is not made to commercially available industrial raw material, is directly made
With.Therefore this method is stronger to anacardol adaptability to raw material.The method of the present invention does not select alkali metal (Na, K) and inorganic strong alkali
(NaOH, KOH etc.), and the alkali metal alcoholates (sodium methoxide, sodium ethoxide etc.) for using alkalinity weaker are anti-as anacardol ethoxylation
The catalyst answered.Reacting balance is controllable, and the process conditions such as temperature, pressure are milder, and reaction product viscosity is relatively low, molecular weight
Narrow distribution (sees attached list 1), and double bond loss is small (seeing attached list 2, double bond retention rate is 92~98%), and product color is shallow, quality
It is good.The method of the present invention can be according to using needs, and the ethylene oxide molecule number of addition is intended in design, hydrophilic to adjust the oleophylic of product
It balances (HLB value), is made and is applicable to the products such as emulsifier, wetting dispersing agent, levelling agent, the detergent of related field.
The method of the present invention has realized industrial applications, related cardanol polyoxyethylene ether product with for farm chemical emulgent,
The functional aids such as metal surface greasy dirt cleaning agent.
Specific embodiment
Below by test examples, a kind of method for preparing cardanol polyoxyethylene ether of the present invention is illustrated
Embodiment 1 (preparation of BGF-10EO-A)
In autoclave put into 304 grams of anacardols, 1.116 grams of sodium methoxides, then by inflated with nitrogen, vacuumize displacement kettle in air
3 times.Start to stir lower heated material, and in 90~120 DEG C of dehydrated under vacuum 45MIN.Then it is initially added into epoxy under negative pressure
Ethane, maintains 130~165 DEG C of reaction temperature, and pressure -0.08~0.26MPa finishes 440 grams of ethylene oxide in 2.5h.So
Negative pressure in slaking reaction 50MIN. to kettle is carried out afterwards.Then residual gas in kettle is removed under 125 DEG C, -0.08MPa vacuum.Drop
Temperature adds in 1.9 grams of lactic acid to 80 DEG C and neutralizes material to PH~6, and discharge to obtain 734 grams of product BGF-10EO-A.
Embodiment 2 (preparation of BGF-20EO-A)
In autoclave put into 250 grams of anacardols, 1.5 grams of sodium methoxides, then by inflated with nitrogen, vacuumize displacement kettle in air 3
It is secondary.Start to stir lower heated material, and in 90~120 DEG C of dehydrated under vacuum 45MIN.Then it is initially added into epoxy under negative pressure
Ethane, maintains 130~165 DEG C of reaction temperature, and pressure -0.08~0.25MPa finishes 735 grams of ethylene oxide in 2.5h.So
After carry out negative pressure in curing insulation reaction 1h to kettle.Then residual gas in kettle is removed under 125 DEG C, -0.08MPa vacuum.Drop
Temperature adds in 2.5 grams of lactic acid to 80 DEG C and neutralizes material to PH~6, and discharge to obtain 976 grams of product BGF-20EO-A.
Embodiment 3 (preparation of BGF-30EO-A)
In autoclave put into 220 grams of anacardols, 1.8 grams of sodium ethoxides, then by inflated with nitrogen, vacuumize displacement kettle in air 3
It is secondary.Start to stir lower heated material, and in 90~120 DEG C of dehydrated under vacuum 45MIN.Then it is initially added into epoxy under negative pressure
Ethane, maintains 130~165 DEG C of reaction temperature, and pressure -0.08~0.24MPa finishes 968 grams of ethylene oxide in 3.0h.So
After carry out negative pressure in curing insulation reaction 1h to kettle.Then residual gas in kettle is removed under 125 DEG C, -0.08MPa vacuum.Drop
Temperature adds in 2.4 grams of lactic acid to 85 DEG C and neutralizes material to subacidity, and discharge to obtain 1178 grams of product BGF-30EO-A.
Comparative example 1 (preparation of BGF-20EO-B).
In autoclave put into 250 grams of anacardols, 1.5 grams of potassium hydroxide, then by inflated with nitrogen, vacuumize displacement kettle in
Air 3 times.Start to stir lower heated material, and in 90~120 DEG C of dehydrated under vacuum 45MIN.Then it is initially added under negative pressure
Ethylene oxide, maintains 140~165 DEG C of reaction temperature, and pressure -0.08~0.25MPa finishes 735 grams of epoxy second in 2.5h
Alkane.Then negative pressure in curing insulation reaction 1h to kettle is carried out.Then residue gas in kettle is removed under 125 DEG C, -0.08MPa vacuum
Body.It is cooled to 80 DEG C of 1.6 grams of addition glacial acetic acid and neutralizes material to subacidity (PH~6), discharge to obtain product BGF- 20EO-B 975
Gram.
Comparative example 2 (preparation of BGF-30EO-B)
In autoclave put into 220 grams of anacardols, 1.8 grams of potassium hydroxide, then by inflated with nitrogen, vacuumize displacement kettle in air
3 times.Start to stir lower heated material, and in 90~120 DEG C of dehydrated under vacuum 45MIN.Then it is initially added into epoxy under negative pressure
Ethane, maintains 140~167 DEG C of reaction temperature, and pressure -0.08~0.22MPa finishes 968 grams of ethylene oxide in 3.0h.So
After carry out negative pressure in curing insulation reaction 1h to kettle.Then residual gas in kettle is removed under 125 DEG C, -0.08MPa vacuum.Drop
Temperature to 85 DEG C of 2.0 grams of addition glacial acetic acid neutralize material to subacidity (PH~6), and discharge to obtain 1173 grams of product BGF-30EO-B.
1 gel permeation chromatography of subordinate list (GPC) method measures the molecular weight distribution data of BGF samples
The double bond retention rate data of subordinate list 2BGF samples
3 anacardol quality analysis list of subordinate list
The name of an article：Anacardol (superfine) lot number：The 105501627TT dates：On May 27th, 2017 production and sales business：Five road junction of Zhejiang
Biomaterial Co., Ltd
Claims (4)
1. a kind of cardanol polyoxyethylene ether, which is characterized in that it has following molecular structure：
Wherein, n=2~30,
R is the hydrocarbon chain containing 15 carbon atoms, can be the saturated hydrocarbon chain that is expressed as below or containing monoene, diene, triolefin respectively
Aliphatic unsaturated hydrocarbon：C15H31, C15H29, C15H27, C15H25.
2. the preparation method of cardanol polyoxyethylene ether as described in claim 1, which is characterized in that in a voltage-resistant reactor
In, raw material anacardol and ethylene oxide, under catalyst action, temperature-pressure carries out polymerisation, and anacardol polyoxy second is made
Alkene ether,
Its specific preparation process is：
1. under room temperature, raw material anacardol and alkoxide catalysis are put into the reactor, with inflated with nitrogen and vacuumizes metathesis reactor
Interior air 3~4 times；
2. 90~120 DEG C are calorified under stirring, 0.5~1.0h of vacuum dehydration；
3. after being evacuated to certain negative pressure, under the conditions of 130~165 DEG C of temperature, 0.1~0.3MPa of pressure, with anacardol and ring
The molar ratio 1 of oxidative ethane:2~30 ratio is passed through ethylene oxide, and ethoxylation is completed in 2~4h；
4. reaction mass is cooled to proper temperature, directly discharge after being neutralized to subacidity with lactic acid, being made has as shown in Equation 1
Molecular structure, the addition cardanol polyoxyethylene ether product of certain ethylene oxide molecule number.
3. the method for preparing cardanol polyoxyethylene ether as described in right 2, which is characterized in that the raw material anacardol is city
Industrial goods are sold, there is certain degree of unsaturation.
4. the method for preparing cardanol polyoxyethylene ether as described in right 2, which is characterized in that the alkoxide catalysis is first
The mixture of any one or two of which in sodium alkoxide, sodium ethoxide, potassium propoxide, the dosage of the catalyst is reaction-ure mixture
0.1~0.3%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710997443.6A CN108129651A (en) | 2017-10-16 | 2017-10-16 | A kind of method for preparing cardanol polyoxyethylene ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710997443.6A CN108129651A (en) | 2017-10-16 | 2017-10-16 | A kind of method for preparing cardanol polyoxyethylene ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108129651A true CN108129651A (en) | 2018-06-08 |
Family
ID=62389620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710997443.6A Pending CN108129651A (en) | 2017-10-16 | 2017-10-16 | A kind of method for preparing cardanol polyoxyethylene ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108129651A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109158050A (en) * | 2018-09-10 | 2019-01-08 | 上海邦高化学有限公司 | Cashew nut phenolic anion-nonionic surfactant and the preparation method and application thereof |
| CN110922581A (en) * | 2019-12-18 | 2020-03-27 | 胡超红 | Processing method of polyoxyethylene ether |
| CN113087894A (en) * | 2021-04-01 | 2021-07-09 | 上海邦高化学有限公司 | Cardanol polyoxyethylene ether, preparation method and application thereof |
| CN114687212A (en) * | 2022-04-20 | 2022-07-01 | 浙江传化化学品有限公司 | High-temperature-resistant wear-resistant spinning oil and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449984A (en) * | 2013-09-24 | 2013-12-18 | 浙江皇马科技股份有限公司 | Anacardol polyoxyethylene ether and preparation method thereof |
| CN106380378A (en) * | 2016-08-26 | 2017-02-08 | 石家庄市海森化工有限公司 | Preparation method of environment-friendly low-foam natural phenol polyoxyethylene ether |
-
2017
- 2017-10-16 CN CN201710997443.6A patent/CN108129651A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449984A (en) * | 2013-09-24 | 2013-12-18 | 浙江皇马科技股份有限公司 | Anacardol polyoxyethylene ether and preparation method thereof |
| CN106380378A (en) * | 2016-08-26 | 2017-02-08 | 石家庄市海森化工有限公司 | Preparation method of environment-friendly low-foam natural phenol polyoxyethylene ether |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109158050A (en) * | 2018-09-10 | 2019-01-08 | 上海邦高化学有限公司 | Cashew nut phenolic anion-nonionic surfactant and the preparation method and application thereof |
| CN110922581A (en) * | 2019-12-18 | 2020-03-27 | 胡超红 | Processing method of polyoxyethylene ether |
| CN110922581B (en) * | 2019-12-18 | 2022-07-08 | 连云港石化有限公司 | Processing method of polyoxyethylene ether |
| CN113087894A (en) * | 2021-04-01 | 2021-07-09 | 上海邦高化学有限公司 | Cardanol polyoxyethylene ether, preparation method and application thereof |
| CN113087894B (en) * | 2021-04-01 | 2022-10-21 | 上海邦高化学有限公司 | Cardanol polyoxyethylene ether, preparation method and application thereof |
| CN114687212A (en) * | 2022-04-20 | 2022-07-01 | 浙江传化化学品有限公司 | High-temperature-resistant wear-resistant spinning oil and preparation method thereof |
| CN114687212B (en) * | 2022-04-20 | 2024-02-09 | 浙江传化化学品有限公司 | High-temperature-resistant wear-resistant spinning oil and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108129651A (en) | A kind of method for preparing cardanol polyoxyethylene ether | |
| CN101509196B (en) | Method of preparing epoxy modified amino-silicone oil softening agent | |
| CN102838313B (en) | Polycarboxylic acid series high molecular synthetic cement grinding additive and preparation method thereof | |
| CN104230724B (en) | A kind of preparation method of diethanol monoisopropanolamine | |
| CN101941894A (en) | Cardanol polyoxyethylene ether and preparation method thereof | |
| US11639418B2 (en) | Synthesis process for one-step production of monomeric polyether for polycarboxylic acid water reducing agents | |
| CN101690877B (en) | Pentadecyl phenol polyethenoxy ether strong biodegradable surfactant | |
| CN101700964B (en) | Water reducing agent, preparation method thereof and maleic acid mono alkyl ester polyether | |
| CN110982056B (en) | Method for synthesizing alkynediol block polyether | |
| CN104437235B (en) | Long chain cation gemini surfactant and preparation method thereof | |
| CN104231257B (en) | A kind of aryl alkyl alcohol polyoxyethylene polyoxypropylene block copolymer and its preparation method and application | |
| CN107537185A (en) | A kind of self-emulsifying type defoamer and preparation method thereof | |
| CN102351664B (en) | Preparation method of pentadecylphenol polyoxyethylene ether high-biodegradability surfactant | |
| CN110452369B (en) | Isomeric alcohol block polyether with excellent oil removal emulsifying performance and preparation method and application thereof | |
| CN111214852B (en) | Biodegradable defoaming agent and preparation method thereof | |
| KR20220148332A (en) | Alkoxylated secondary alcohol | |
| CN101885839A (en) | Method for preparing blocked allyl polyether | |
| CN103951794A (en) | Low-foam polycarboxylate dispersant and its preparation method | |
| CN103951798A (en) | Polycarboxylate dispersant and its preparation method | |
| CN107459709A (en) | A kind of high-strength abrasion-proof plastics | |
| CN101941893B (en) | Method for synthesizing tripropylene glycol | |
| CN103012079A (en) | Method for synthesizing ethylene glycol allyl ether under catalysis of solid base catalyst | |
| CN106590729B (en) | A kind for the treatment of process of softening oil | |
| CN103936993A (en) | Method for preparing methyl silicone oil by utilizing sulfuric acid | |
| CN107400230A (en) | A kind of high efficient cryogenic petroleum demulsifier and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180608 |
|
| RJ01 | Rejection of invention patent application after publication |